Amino-containing delta-lactone compound and preparation method thereof

A compound and compound structural formula technology, applied in the field of amine group-containing delta-lactone compounds and their preparation, can solve the problems of unachieved enantioselective transformation and the like

Active Publication Date: 2021-09-10
NORTHEAST NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] (1) The method needs to use an electrophilic halogenating reagent, and the synthesized product contains a halogen atom; (2) the synthesized product of the method is a 5-membered ring lactone; (3) although the synthesized compound of the method contains Chiral carbon atoms, but all are racemized products without enantioselective conversion

Method used

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  • Amino-containing delta-lactone compound and preparation method thereof
  • Amino-containing delta-lactone compound and preparation method thereof
  • Amino-containing delta-lactone compound and preparation method thereof

Examples

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preparation example Construction

[0058] The present invention also provides a preparation method for synthesizing δ-lactone compounds containing amine groups, the method comprising:

[0059] The aryl cyclopropane with the ester group or carboxyl side chain of the structural formula shown in formula 1 is used as the reaction raw material, and the nitrogen-fluorobisbenzenesulfonamide (NFSI) is used as the oxidant and the nucleophilic nitrogen source, in the catalyst, the ligand and the solvent Under the effect of reacting, obtain the δ-lactone compound containing amino group shown in formula 2;

[0060]

[0061] In formula 1 and formula 2, R represents hydrogen (H), 6-methyl (6-methyl), 7-methyl (7-methyl), 8-methyl (8-methyl), 6-methoxy ( 6-methoxy), 7-methoxy (7-methoxy), 6-chloro (6-Cl), 7-chloro (7-Cl), 6-fluoro (6-F), 7-fluoro (7-F ), 8-fluoro (8-F) or 6,8-difluoro (6,8-difluoro);

[0062] R 1 Represents bis-benzenesulfonamide (N(SO 2 Ph) 2 );

[0063] R 2 Represents methyl (methyl), hydrogen (H) o...

Embodiment 1

[0078] Add 10 mol% copper trifluoromethanesulfonate (Cu(OTf) 2 ), 12mol% of 6,6'-dimethyl-2,2'-bipyridine and 2 ml of dichloromethane, stirred at room temperature for 10 minutes, then added 0.2 mmol of 2-cyclopropyl Methyl phenylacetate and 1.5 times the amount of nitrogen-fluorobisbenzenesulfonamide (NFSI) were transferred to 70° C. for 12 hours after tightening the sealing cap. After the reaction, the pressure tube was cooled to room temperature, quenched by adding water to the system, extracted with dichloromethane (extracted 3 times, each with 10 ml of dichloromethane), the organic phases of the three extractions were combined and then washed with anhydrous sulfuric acid After drying with sodium, the organic solvent was removed using a rotary evaporator, and the resulting crude product was separated by silica gel column chromatography (petroleum ether: ethyl acetate = 6:1) to obtain the aminated lactonization product 1-3a. The product yield that embodiment 1 obtains is 81...

Embodiment 2

[0082] The steps and conditions are the same as in Example 1, except that the reaction raw material 1-1a is replaced with 1-1b. The product yield obtained was 62%. H NMR and C spectra such as image 3 and 4 shown.

[0083] The reaction process is as follows:

[0084]

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Abstract

The invention provides an amino-containing delta-lactone compound and a preparation method thereof, and belongs to the technical field of compound synthesis. The structural formula of the compound is shown as a formula 2. The invention also provides a preparation method of the amino-containing delta-lactone compound. According to the method, aryl cyclopropane which has a structural formula as shown in a formula 1 and is connected with an ester group or carboxyl side chain is used as a reaction raw material, nitrogen fluoro dibenzenesulfonamide is used as an oxidizing agent and a nucleophilic nitrogen source, and reaction is performed under the action of a catalyst, a ligand and a solvent to obtain the amino-containing delta-lactone compound as shown in a formula 2. According to the method, light / copper combined catalysis of cyclopropane ring opening asymmetric lactonization is realized, and a stereospecific 6-membered lactone product is obtained with the yield of 75% and the ee value of 81%.

Description

technical field [0001] The invention belongs to the technical field of compound synthesis, and in particular relates to a delta-lactone compound containing an amino group and a preparation method thereof. Background technique [0002] In the prior art, the method for synthesizing middle-ring lactone compounds starts from cyclopropane compounds containing ester groups or carboxyl groups, and cyclopropane ring-opening halogenated lactonization reactions occur under the drive of electrophilic halogenating reagents to synthesize various Functionalized lactone compounds. (China H, Kumar R, Kikushima K, et al.Halogen-Induced Controllable Cyclizations as Diverse Heterocycle Synthetic Strategy[J].Molecules,2020,25(24):6007-6029.) This method has the following technical problems: [0003] (1) The method needs to use an electrophilic halogenating reagent, and the synthesized product contains a halogen atom; (2) the synthesized product of the method is a 5-membered ring lactone; (3) a...

Claims

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Application Information

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Patent Type & AuthorityApplications(China)
IPC IPC(8): C07D311/76
CPCC07D311/76
Inventor张茜张前李燕
OwnerNORTHEAST NORMAL UNIVERSITY